Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
  • G03G5/0528—Macromolecular bonding materials
  • G03G5/0532—Macromolecular bonding materials obtained by reactions only involving carbon-to-carbon unsatured bonds
  • G03G5/0546—Polymers comprising at least one carboxyl radical, e.g. polyacrylic acid, polycrotonic acid, polymaleic acid; Derivatives thereof, e.g. their esters, salts, anhydrides, nitriles, amides
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
  • Y10S430/1055—Radiation sensitive composition or product or process of making
  • Y10S430/106—Binder containing
  • Y10S430/111—Polymer of unsaturated acid or ester

Definitions

• the invention relates to light-sensitive recording materials, in particular for the production of planographic printing plates or also resist patterns, with an aqueous-developable - in particular aqueous-alkaline-developable - light-sensitive recording layer applied to a support and containing a polymeric binder.
• Light-sensitive recording materials which can be washed out with water or, in particular, aqueous alkaline media, for the production of planographic printing plates or resist patterns are known. These generally contain, on a dimensionally stable support, for example an aluminum sheet or a plastic film, a light-sensitive recording layer containing a polymeric binder.
• the polymeric binders used here are, in particular in aqueous media, preferably in aqueous-alkaline media, soluble or dispersible copolymers, such as Styrene / maleic anhydride copolymers, styrene / maleic acid half-ester copolymers, (meth) acrylate / (meth) acrylic acid copolymers or copolymers of styrene, (meth) acrylates and (meth) acrylic acid and optionally other comonomers.
• soluble or dispersible copolymers such as Styrene / maleic anhydride copolymers, styrene / maleic acid half-ester copolymers, (meth) acrylate / (meth) acrylic acid copolymers or copolymers of styrene, (meth) acrylates and (meth) acrylic acid and optionally other comonomers.
• the light-sensitive, photopolymerizable recording layer usually contains, in addition to the polymeric binders which are soluble or dispersible in aqueous media, at least one ethylenically unsaturated, photopolymerizable, low-molecular compound, at least one photopolymerization initiator and optionally further additives and / or auxiliary substances, such as, for example Thermal polymerization inhibitors, dyes, pigments, sensitometric regulators, plasticizers, fillers, etc.
• aqueous developable, photopolymerizable recording materials include in DE-B-2 027 467, DE-B-2 064 080, De-A-2 205 146, DE-A-2 602 410 and EP-A-49 502.
• a radiation-polymerizable mixture which can be used for the production of copying material is known which essentially comprises a water-insoluble binder which is soluble or at least swellable in aqueous-alkaline solutions, a polymerization initiator which can be activated by radiation and a polyglycol di contains (meth) acrylate.
• a light-sensitive, photoconductive recording layer is applied to an electrically conductive substrate which, in addition to the polymeric binder which is soluble or dispersible in aqueous media, comprises at least one compound which generates charge carriers or a sensitizer and at least one compound which transports charge carriers and, if appropriate, further additives contains.
• the polymeric binder which is soluble or dispersible in aqueous media comprises at least one compound which generates charge carriers or a sensitizer and at least one compound which transports charge carriers and, if appropriate, further additives contains.
• DE-B-2 718 047 describes photopolymerizable, water-developable mixtures for the production of planographic printing plates or photoresist layers which, as binders, contain a relatively high molecular weight, water-soluble methacrylic acid polymer with at least 70% methacrylic acid units. This makes it possible to develop the recording materials produced with these photopolymerizable mixtures using water alone, but these recording materials also leave something to be desired in terms of their overall property profile and in particular the necessary, relatively long development times.
• the object of the present invention was to demonstrate new, water-developable, light-sensitive recording materials, in particular for the production of planographic printing plates or resist patterns, which are distinguished by a balanced, advantageous combination of properties.
• light-sensitive recording materials which contain in their light-sensitive recording layer as polymeric binder a copolymer which is soluble or at least dispersible in aqueous media and which contains a small proportion of the anhydride of a polymerizable moncarboxylic acid containing at least one ethylenic unsaturation as comonomer built-in contains.
• the invention accordingly relates to a light-sensitive recording material, in particular for the production of planographic printing plates or resist patterns, with a light-sensitive recording layer which contains an aqueous developable - in particular aqueous-alkaline developable - light-sensitive polymeric binder which contains or at least disperses polymeric binder in aqueous media - in particular aqueous-alkaline media , which is characterized in that a copolymer which contains an anhydride of a polymerizable, ethylenically unsaturated monocarboxylic acid in an amount of 0.05 to 2% by weight, preferably in an amount of 0.1 to 1% by weight, is contained in the light-sensitive recording layer as a polymeric binder based on the copolymer, contains copolymerized as comonomer.
• light-sensitive recording materials are understood to mean both the recording materials with a light-sensitive, photopolymerizable recording layer and the recording materials with a light-sensitive, electrophotographic recording layer, as described, e.g. are described in the publications cited at the beginning.
• the polymeric binders contained according to the invention in the light-sensitive recording layers of these recording materials are copolymers which are soluble or dispersible in aqueous media, in particular in aqueous-alkaline media.
• the comonomers described for this purpose in the literature can be used to construct these copolymers.
• these are copolymers of one or more vinyl monomers, which as such form water-insoluble polymers, with one or more monomers with free acid groups, in particular sulfonic acid or carboxyl groups, or with cyclic anhydride groups, in particular cyclic ones Anhydrides of ethylenically unsaturated dicarboxylic acids.
• vinyl monomers examples include: vinyl aromatics, such as Styrene, substituted styrenes which are substituted in the side chain or in the core, for example by alkyl groups or halogen atoms, such as a-methylstyrene, o- or p-chlorostyrene, vinyltolul and the like; Esters and amides of acrylic acid or methacrylic acid, e.g.
• Acrylates or methacrylates of alkanols with 1 to 20 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, hydroxyalkyl (meth) acrylates, in particular with 2 to 6 carbon atoms in the hydroxyalkyl radical, glycidyl (meth) acrylate, (meth) acrylamide and derivatives thereof and the like; (Meth) acrylonitrile; Vinyl acetate, vinyl propionate; Vinyl chloride; Vinyl alkyl ketones, in particular with 1 to 4 carbon atoms in the alkyl radical; Vinyl alkyl ethers, in particular with 1 to 8 carbon atoms in the alkyl radical.
• the second group of comonomers with the acidic groups such as sulfonic acid or free carboxyl groups, or cyclic anhydride groups
• Other comonomers for the copolymers to be used according to the invention are also N-vinyl lactams, such as in particular N-vinyl pyrrolidone and N-vinyl caprolactam.
• the copolymers to be used as binders also contain 0.05 to 2% by weight, based on the copolymer, of an anhydride of a polymerizable monocarboxylic acid containing ethylenic unsaturation as a further comonomer. If the proportion of these comonomers in the copolymer is below 0.05% by weight, there is no appreciable influence on the properties of the light-sensitive recording layer. If the content of these comonomers in the copolymer exceeds 2% by weight, the copolymers are generally no longer suitable for use in light-sensitive recording layers.
• the anhydrides of polymerizable ethylenically unsaturated monocarboxylic acids include, in particular, acrylic anhydride and methacrylic anhydride. These also include, for example, crotonic anhydride, dimethylacrylic anhydride, and anhydrides of hydroxycarboxylic acids, e.g.
• the latter group of comonomers includes, for example, (meth) acrylic amidoglycolic anhydride and glycolic anhydride di (meth) acrylate.
• Preferred polymeric binders for the light-sensitive recording materials are copolymers which are soluble or dispersible in aqueous media, in particular aqueous-alkaline media, and which, in addition to the proportion according to the invention of the anhydride of an ethylenically unsaturated monocarboxylic acid, comprise at least one, but preferably two or more, monomers as comonomers from the group styrene, alkyl (meth) acrylates, (methlacrylamide, hydroxyalkyl (methlacrylate, vinyl acetate, N-vinylpyrrolidone, (methlacrylic acid, maleic anhydride and maleic acid semiesters) in copolymerized form.
• copolymers which, in addition to the proportion of the anhydride according to the invention, of an ethylenically unsaturated monocarboxylic acid are also very suitable optionally further comonomer building blocks containing the following comonomers in copolymerized form: styrene and maleic anhydride; styrene and maleic acid half-ester; styrene, maleic anhydride and maleic acid half-ester; styrene, maleic anhydride and acrylic acid acid and / or preferably methacrylic acid; (Meth) acrylic acid ester and acrylic acid and / or preferably methacrylic acid; Styrene, (meth) acrylic acid ester, and acrylic acid and / or preferably methacrylic acid.
• the preferred anhydride of an ethylenically unsaturated monocarboxylic acid is acrylic acid anhydride, methacrylic acid anhydride or crotonic acid anhydride.
• Copolymers which have proven particularly favorable are those which contain 5 to 70% by weight of styrene, 5 to 50% by weight of acrylic acid and / or preferably methacrylic acid, 5 to 50% by weight of maleic anhydride, 0.05 to 2% by weight % Acrylic anhydride or preferably methacrylic anhydride and 0 to 30 wt .-% of other comonomers, such as Containing vinyl acetate, (meth) acrylic acid ester or the like in copolymerized form, the percentages being based in each case on the weight of the copolymer.
• copolymers to be used according to the invention as a polymeric binder differ in their composition from the known polymeric binders of this type essentially only by the incorporation of a small amount of an anhydride of a polymerizable monocarboxylic acid containing ethylenic unsaturation and, in connection therewith, by a comparatively higher molecular weight.
• the photosensitive recording layers produced with the copolymers according to the invention as binders are distinguished from the known materials by improved mechanical properties without the development times or other properties being impaired.
• the copolymers to be used according to the invention can be prepared by copolymerization of the comonomers by the known and customary polymerization methods.
• the copolymerization can be carried out, for example, by the solution or the precipitation polymerization method.
• solution polymerization e.g. Tetrahydrofuran, dimethoxyethane, dioxane or ethyl acetate as solvent
• the total concentration of the monomers should preferably be between 25 and 45% by weight, based on the solution.
• Aliphatic or aromatic hydrocarbons are suitable as inert solvents for precipitation polymerization; the concentration of the monomers is generally adjusted between 5 and 25% by weight.
• the usual free radical initiators, such as, for example, azobisisobutyronitrile, are suitable as polymerization initiators.
• the polymerization temperature is generally between 50 and 100 ° C, preferably between 75 and 95 ° C.
• the choice of the copolymer essentially depends on the further composition of the light-sensitive recording layer and its desired application properties. In principle, it can be carried out according to the same or similar criteria as with the known materials of the type in question and is therefore easy and easy for the person skilled in the art to determine, if necessary on the basis of a few simple preliminary tests.
• the copolymers to be used as binders can easily be adapted to the compounds carrying charge carriers contained in the photoconductive recording layers.
• light-sensitive recording materials with a light-sensitive, photopolymerizable recording layer generally contain, in addition to the polymeric binders according to the invention, at least one ethylenically unsaturated, photopolymerizable, low-molecular compound, at least one photopolymerization initiator or a photopolymerization initiator system and, if appropriate, further additives and / or auxiliaries for improvement and / / or modification of the general properties of the recording layers or of the planographic printing plates or resist patterns produced therefrom.
• such light-sensitive, photopolymerizable recording layers contain, for example, 40 to 90% by weight of the binder according to the invention, 5 to 50% by weight of ethylenically unsaturated, photopolymerizable, low molecular weight compounds, 0.5 to 10% by weight of at least one photoinitiator or photoinitiator system, 0 to 8% by weight, preferably 0.01 to 5% by weight, of auxiliaries influencing the exposure and / or polymerization properties, such as, for example Dyes, sensitometric regulators, thermal polymerization inhibitors, etc., and 0 to 20% by weight of additives which improve or modify the mechanical properties, such as plasticizers, fillers, flow control agents, further, indifferent, high or low molecular weight polymers, etc., the Percentages always refer to the entire recording layer.
• Suitable ethylenically unsaturated, photopolymerizable low-molecular compounds are both monomers and oligomers (with a molecular weight of up to about 5000, in particular with a molecular weight of up to about 3000), which can be both mono- or polyfunctional, ie one or more photopolymerizable, ethylenic May have double bonds.
• the light-sensitive, photopolymerizable recording layer contains bi- or polyfunctional ethylenically unsaturated, photopolymerizable, low molecular weight compounds alone or mixtures thereof with monofunctional ethylenically unsaturated, photopolymerizable, low molecular weight compounds.
• ethylenically unsaturated, photopolymerizable, low molecular weight compounds that can be used alone or in a mixture with one another include the allyl and vinyl compounds, in particular the derivatives of (meth) acrylic acid and very particularly the (meth) acrylic acid esters.
• Examples of very suitable ethylenically unsaturated, photopolymerizable, low molecular weight compounds are the di- and tri (meth) acrylates of ethylene glycol, diethylene glycol, triethylene glycol or polyethylene glycols with a molecular weight of up to about 500, 1,2-propanediol, 1,3-propanediol, 1 , 4-butanediol, 1,1,1-trimethylolpropane, neopentyl glycol (2,2-dimethylpropanediol), glycerin or pentaerythritol; Glucose or tetra (meth) acrylate; furthermore the monoacrylates and monomethacrylates of the diols and polyols mentioned, such as, for example, ethylene glycol, di-, tri- or tetraethylene glycol mono (meth) acrylate and the (meth) acrylates of monoalkanols, in particular with
• photoinitiators for the light-sensitive, photopolymerizable recording layers are the photoinitiators or photoinitiator systems known for the production of offset printing plates or resist layers.
• suitable photoinitiators include compounds such as benzoin, the benzoin derivatives such as benzoin ethers, the substituted benzoin, substituted benzoin derivatives, e.g.
• substituted benzoin ethers the benzilene, in particular benzil ketal, or the acylphosphine oxide compounds, in particular compounds of the benzophenone type and its derivatives, such as benzophenone, 4,4'-dimethyiaminobenzophenone, 4,4'-diethylaminobenzophenone, derivatives of Michler's ketone, 4,4 ' -Dichlorobenzophenone etc.
• Anthraquinones such as 2-ethylanthraquinone, t-butylanthraquinone, etc .
• Bisimidazole derivatives such as 2,4,5-triarylimidazole dimers
• 2-chlorothioxanthone and the acridine or phenazine derivatives effective as photoinitiators.
• Examples of initiator systems are combinations of the initiators mentioned with sensitization aids, such as, in particular, tertiary amines.
• Typical examples of such initiator systems are combinations of benzophenone or benzophenone derivatives with tertiary amines, such as triethanolamine or Michler's ketone; or mixtures of 2,4,5-triarylimidazole dimers and 2-mercaptobenzoquinazole, leuco crystal violet, tris (4-diethylamino-2-methylphenyl) methane and the like.
• tertiary amines such as triethanolamine or Michler's ketone
• 2,4,5-triarylimidazole dimers and 2-mercaptobenzoquinazole leuco crystal violet
• tris (4-diethylamino-2-methylphenyl) methane and the like tris (4-diethylamino-2-methylphenyl) methane and the like.
• additives and / or auxiliaries for the light-sensitive, photopolymerizable recording layers are, on the one hand, dyes and / or pigments, which can act both as a contrast agent and as a layer-strengthening agent.
• Suitable dyes such as those described in US Pat. Nos.
• 3,218,167 and 3,884,693 include, for example, Victoria Pure Blue FGA, Victoria Pure Blue BO (CI 42 959), Malachite Green, Crystal Violet, Victoria Blue B ( CI 44 045), Rhodamine-6 GDN (Cl 45 160) and others, as well as the leuco bases of the triarylmethane dyes, such as, for example Malachite green leuco base, crystal violet leuco base, or rhodamine B base.
• additives and / or auxiliaries also include thermal polymerization inhibitors, such as Hydroquinone, hydroquinone derivatives, 2,6-di-t-butyl-p-cresol, nitrophenols, N-nitrosoamines such as N-nitrosodiphenylamine or the salts of N-nitrosocyclohexylhydroxylamine.
• the light-sensitive, photopolymerizable recording layers may also contain, for example, the sensitometric regulators described in the literature, such as 9-nitroanthracene, 10,10'-bisanthrone, phenazinium, phenoxazinium, acridinium or phenothiazinium dyes, 1,3-dinitrobenzenes and the like.
• additives and / or auxiliary substances there are e.g. fillers, reinforcing agents, further binders, plasticizers, flow control agents and the like which improve the mechanical properties are also considered.
• the light-sensitive, photopolymerizable recording layers can be produced by the methods known per se; they are advantageously applied to the respective carrier material from a solution that is as homogeneous as possible in a suitable organic solvent in such a way that a dry layer thickness of approximately 0.1 to 50 ⁇ m results after the solvent has been vented.
• the dry layer thickness depends essentially on the application of the light-sensitive materials and is in the range from 0.7 to 3.5 1 1m for the production of planographic printing plates. Both very thin layers and thicker layers of resist, for example in the range from about 5 to 50 11 m, can be used to produce resist patterns.
• the light-sensitive, electrophotographic recording materials with a light-sensitive, photoconductive recording layer contains, in addition to the binders according to the invention in a homogeneous distribution, at least one compound which transports charge carriers, at least one compound which produces charge carriers upon actinic exposure or a sensitizer and, if appropriate, further indifferent ones, the application technology and in particular the mechanical ones Properties improving or modifying additives and / or auxiliary substances.
• the photosensitive, photoconductive recording layer contains, for example, 45 to 75% by weight of the binder according to the invention and 25 to 50% by weight of the charge carriers Compounds, 0.05 to 2% by weight of the charge carrier-producing compounds or the sensitizers and 0 to 25% by weight of further, conventional additives and / or auxiliaries, in particular improving and / or modifying the mechanical properties of the recording layer, where the percentages each relate to the entire photosensitive, photoconductive recording layer. If further additives and / or auxiliaries are contained therein, their proportion is generally at least 2% by weight, based on the recording layer.
• the compounds and substances known and customary for electrophotographic recording materials with single-layer, photoconductive recording layers as described, inter alia, in the literature cited at the outset.
• Both low molecular weight and polymeric aromatic and heterocyclic compounds can be used as the charge carriers of the electrical current. Mention may be made of oxazole derivatives (DE-B-1 120 875), oxdiazole derivatives (DE-B-1 058 836), triazole derivatives (DE-B-1 060 260), azomethines (US-A-3 041 165), pyrazoline derivatives (DE -B-1 060 714) and imidazole derivatives (DE-B-1 106 599).
• Benzotriazole derivatives have proven to be very advantageous, in particular 2- (4'-aminophenyl) benzotriazoles-1,2,3, such as those e.g.
• Hydrazone derivatives such as those e.g. are listed in DE-A-3 201 202.
• polymer charge transport compounds are also suitable.
• the charge carriers of the electrical current-transporting compounds should generally be well compatible in the required amount with the polymeric binder of the light-sensitive, photoconductive recording layer.
• Compounds or sensitizers which generate charge carriers for the light-sensitive, single-layer photoconductive recording layers according to the invention are in particular the known and known sensitizing dyes, such as Triarylmethane series dyes, xanthene dyes and cyanine dyes.
• Senitizing dyes such as Triarylmethane series dyes, xanthene dyes and cyanine dyes.
• Very good results were obtained with rhodamine B (CI 45 170), rhodamine 6 G, (CI 45 160), malachite green (CI Basic Green 4; CI 42 000), methyl violet (CI 42 535), crystal violet (CI 42 555), astrazone orange R (CI 48 040), CI Basic Red 12 (C.I. 48 070), C.I. Fanal Violet 3 R supra or Astragelb R (C.I. Basic Yellow 44).
• the sensitizing dyes can be used alone or in a mixture with one another, in order to achieve panchromatic sensitization it can be advantageous to use mixtures of sensitizing dyes which absorb in different wavelength ranges of actinic light, for example mixtures of triarylmethane dyes and cyanine dyes.
• the photosensitive, photoconductive recording layer of the electrophotographic recording materials can contain additives which are customary for the particular use, e.g. Leveling agents, plasticizers and other high or low molecular weight polymers.
• the usual and known methods can be used to produce the photosensitive, photoconductive recording layers; they are advantageously applied to the respective carrier material from an approx. 5% by weight solution in a suitable solvent in such a way that after the solvent has been vented, a dry layer thickness of approx. 0.1 to 50 ⁇ m (depending on the intended use, for electrographic Printing forms, in particular planographic printing plates, preferably about 1 to 6 1 1m) results.
• Suitable supports for the light-sensitive recording layers are the dimensionally stable, rigid or preferably flexible layer supports which are customary and known per se for light-sensitive recording materials of the type in question, the type of layer support also being determined by the intended use.
• all electrically conductive carrier materials can be used as carriers for light-sensitive electrophotographic recording materials, provided they are suitable for the respective field of application.
• Metallic supports, for example, are preferred for the light-sensitive materials according to the invention.
• a cover layer or cover film can also be arranged on the light-sensitive recording layer, which preferably is soluble in the same developer solvent as the photosensitive recording layer or is peelable from it before development.
• This cover layer or cover film primarily serves to protect the photosensitive recording layer during storage and handling of the photosensitive recording materials and also as an oxygen barrier for the photosensitive photopolymerizable recording layers. Cover layers made of polyvinyl alcohols or polyvinyl alcohol derivatives or cover sheets made of polyolefins, such as polyethylene, have proven to be particularly suitable.
• the photosensitive recording materials according to the invention are advantageously suitable for the production of planographic printing forms or resist patterns according to the processes known per se and customary for this.
• the recording layer is first exposed imagewise with actinic light, with the usual light sources of actinic light such as UV fluorescent tubes, high-pressure, medium or low-pressure mercury lamps, superactinic fluorescent tubes, xenon being used for this -Impulse lamps, but also UV lasers, argon lasers and the like are suitable.
• the wavelength emitted by the light sources should generally be between 230 and 450 nm, preferably between 300 and 420 nm, and in particular should be matched to the self-absorption of the photoinitiator contained in the light-sensitive recording layer.
• the imagewise exposure to actinic light triggers a photopolymerization in the exposed areas of the recording layer, which leads to crosslinking and thus differentiation in solubility between the exposed and unexposed layer areas.
• the planographic printing form or the resist pattern is developed by washing out the unexposed, uncrosslinked regions of the recording layer with a suitable developer solvent.
• planographic printing forms by means of the photosensitive, electrophotographic recording materials according to the invention is carried out, as usual, by electrostatically charging the electrophotographic recording material using a high-voltage corona, immediately following image-wise exposure of the photoconductive recording layer to actinic light, developing the present electrostatic, latent charge image using a dry or Liquid toner, the fixing of the toner, for example by a subsequent melting process, and the removal of the unstressed regions of the photoconductive recording layer by means of a suitable washing-out agent.
• the shape thus obtained can then be prepared in a known manner for offset printing, e.g. through hydrophilization and rubber coating of the water-bearing surface.
• the image-wise exposed recording materials can be developed or washed out by spraying, washing, rubbing, brushing, etc. with the developer solvent.
• aqueous solvents such as e.g. Water or mixtures of water with organic solvents, such as, for example, alcohols, and in particular aqueous alkaline solutions, are suitable for setting the most favorable pH, generally in the range from 8 to 14, preferably in the range from 9 to 12, alkaline substances, such as Borax, disodium hydrogen phosphate, soda or alkali hydroxides or organic bases such as di- or triethanolamine.
• the aqueous alkaline developer solutions can also contain buffer salts, e.g. contain water-soluble alkali phosphates, silicates, borates, acetates or benzoates.
• Wetting agents preferably anionic wetting agents, and optionally water-soluble polymers, such as e.g. Sodium carboxymethyl cellulose, polyvinyl alcohol, polysodium acrylate and the like can also be used.
• the aqueous alkaline developer solvents also contain additions of water-soluble organic solvents, such as e.g. aliphatic alcohols, acetone or tetrahydrofuran.
• the photosensitive recording materials according to the invention are distinguished by a combination of very good properties, in particular by good mechanical properties and high durability in use with good exposure properties and in particular short washout times. They are therefore particularly suitable for all areas of application in reprography, where easy washability and a high mechanical level are desired.
• the invention is further illustrated by the following examples. Unless stated otherwise, the parts and percentages in the examples relate to the weight.
• the K value according to Fikentscher (measured in a 1% solution of the respective polymer in tetrahydrofuran) was determined as a measure of the molecular weight of the polymers.
• This solution was applied in such a layer thickness to an offset-typical aluminum carrier sheet that a dry layer thickness of 3.5 11 m resulted after the solvent had been vented off.
• This electrophotographic plate was electrostatically charged to -600 V on the surface, then exposed imagewise with an illuminance of 8 ⁇ W cm- 2 in the layer plane for 15 seconds, and emphasized with a commercially available powder toner. After the toner fixation, the unstressed areas of the electrophotographic layer were washed off with a mixture of 0.5% soda, 25% isopropanol and 74.5% water, thereby exposing the aluminum surface. After the gumming, this plate was printed directly in an offset machine. Flawless print quality was achieved, and no signs of abrasion could be seen even after long printing times.
• the recording material thus produced was exposed with a 5 kW high-pressure halide burner at a distance of 1 m for 5.5 seconds through a standard negative.
• the exposed plate was then washed out with an aqueous alkaline solution with a pH of 11.6 in a continuous washer in 25 seconds.
• the offset printing plate thus obtained was used in an offset printing machine to achieve excellent printing results without any visible signs of wear.
• a solution was first prepared from the following components: 67 parts of a copolymer of 48% styrene, 19% maleic anhydride, 32.6% acrylic acid and 0.4% methacrylic anhydride (K value: 53.5), 22 parts of trimethylolpropane triacrylate , 11 tetraethylene glycol dimethacrylate, 3 parts benzophenone, 0.3 part Michler's ketone, 0.05 part crystal violet leuco base and 140 parts tetrahydrofuran.
• This solution was poured onto a 0.025 mm thick polyester film in such a way that after drying in air a dry layer thickness of about 25 ⁇ m resulted. The dried layer was then covered with an approximately 25 11 m thick polyethylene film.
• the photopolymerizable layer was laminated onto a copper circuit board, as is customary for the production of printed circuits, at 120 ° C. under pressure.
• the photopolymerizable layer was then exposed imagewise through the polyester film using a corresponding photomask with the pattern of the conductor tracks of a printed circuit.
• the exposure was carried out with a 400 W / 50 A mercury vapor lamp at a distance of 30 cm with an exposure time of 45 seconds.
• the polyethylene terephthalate film was then removed and the unexposed areas of the photopolymer layer were washed out for 3.5 minutes with a 2% aqueous sodium carbonate solution. A true-to-the-original resist pattern with well-formed edges was obtained.
• the exposed areas of the copper circuit board that were not covered by the resist pattern could be etched with a ferrichloride solution without problems. After the etching, subsequent rinsing and drying, the resist layer was removed from the remaining copper by immersion in a 3% aqueous sodium hydroxide solution at 70 ° C. for 2 minutes. The result was a high quality printed circuit board.

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• Photosensitive Polymer And Photoresist Processing (AREA)

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• 1985
  • 1985-02-11 EP EP85101429A patent/EP0152889B1/de not_active Expired
  • 1985-02-11 DE DE8585101429T patent/DE3560654D1/de not_active Expired
  • 1985-02-14 US US06/701,536 patent/US4710446A/en not_active Expired - Fee Related
  • 1985-02-15 JP JP60026667A patent/JPS60247638A/ja active Granted

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